CN102476063A - Bifunctional catalyst and application of bifunctional catalyst in preparation of benzil by benzoin dehydrogenation/oxidation - Google Patents
Bifunctional catalyst and application of bifunctional catalyst in preparation of benzil by benzoin dehydrogenation/oxidation Download PDFInfo
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- CN102476063A CN102476063A CN201010566755XA CN201010566755A CN102476063A CN 102476063 A CN102476063 A CN 102476063A CN 201010566755X A CN201010566755X A CN 201010566755XA CN 201010566755 A CN201010566755 A CN 201010566755A CN 102476063 A CN102476063 A CN 102476063A
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Abstract
The present invention relates to a bifunctional catalyst and an application of the bifunctional catalyst in preparation of benzil by benzoin dehydrogenation/oxidation. According to the catalyst, an anion exchange resin or a cation exchange resin is adopted as a carrier; a variable-valence transition metal or a rare earth metal element is bonded on the carrier in a chemical bonding manner, wherein the binding amount of the variable-valence transition metal or the rare earth metal element is 0.5-10% of the weight of the catalyst; the metal element on the carrier is bonded with an acidic ion exchange resin or an alkaline ion exchange resin through chemical bonds, wherein the metal element on the carrier is adopted as an oxidation catalyst; under a certain reaction condition, benzoin is subjected to a dehydrogenation/oxidation process, hydroxyl is transformed into carbonyl, and the measured water is generated. The catalyst has the following advantages that: the use conditions are mild, the product is easy to separate, the catalyst can be used many times, and the like.
Description
Technical field
The present invention develops the catalyst that a kind of benzoin dehydrogenation/oxidation prepares benzil, and this catalyst is that the transition metal that resin supports constitutes, and under the certain reaction condition, the hydroxyl on the benzoin is transformed into carbonyl, generates the process of metering water simultaneously.This catalyst has the service condition gentleness, and product separates easily, repeatedly characteristics such as use.
Background technology
Benzil has another name called diphenylthanedione, is dibenzoyl, dibenzoyl again, is a kind of important Organic Chemicals.Be used for the synthetic of sensitising agent, curing agent, pesticide, medicine and types of functionality material, also be applicable to and make printing-ink that food uses etc., be with a wide range of applications.Domestic benzil industrial process adopts the metering method for oxidation of nitric acid as oxidant usually; But reaction is fierce, emits a large amount of nitrogen oxide gas contaminated environment. be detrimental to health, and the reaction back produces a large amount of spent acid; Reclaiming then increases cost, discharges then contaminated environment; To this situation, recent two decades comes people to carry out broad research, and the research method of the report of seeing mainly contains DMSO/ (COCl)
2/ CH
2Cl
2, (PhCH
2Et
3N) Br
-/ (PhCO)
2O
2/ MeCN, NBS/CCl
4Oxidizing process, H
2O
2Oxidizing process, high-valency metal are made the direct oxidation method of oxidant.These method for oxidation, the subject matter of existence is: the disposable consumption of oxidant, the toxicity that has is big, the expensive that has, operation is numerous and diverse, separates purification difficult, and environmental pollutant discharge is big.Like the metal dichromate oxidizing process, the reaction time reaches more than ten hour, contains high valence chrome in the reactant liquor, and pollution of chromium is inevitable; The iron chloride oxidizing process, FeCl
36H
2O is the good oxidant of oxidation diaryl ethanol ketogenesis diaryl second diketone, yet this technological reaction time is long, and FeCl
36H
2O is prone to the moisture absorption, is difficult to preserve, and is prone to again form colloid with the aqueous solution, makes troubles to post processing.
People such as Zhang Guisheng are carrier with aluminium oxide or silica gel, and a certain amount of dimethylamine hydrochloride chromium trioxide of load is in cyclohexane solvent; The oxidation reaction that is used for benzoin; Can obtain corresponding benzil compounds with high yield, reaction condition is gentle, the product easy separation.But the dimethylamine hydrochloride chromium trioxide is an oxidant stoichiometry; The disposable consumption of oxidant, operation is numerous and diverse, separates purification difficult; Environmental pollutant discharge is big. and after these oxidants are reduced; Generally do not reclaim, increased production cost, bring the handling problem of a large amount of toxic heavy metals simultaneously.
Compare with chromium, the high oxide of transition metal such as iron, manganese has good oxidisability, simultaneously the low advantage of toxicity.Like Iron(III) chloride hexahydrate is the good oxidant that the Oxybenzene acyloin generates benzil, but ferric trichloride is prone to the moisture absorption, is difficult to preserve; Iron ion Yi Yushui again forms colloid; Make troubles to post processing, bring in the product, the color reaction time that influences product is long.Xing Chun bravely waits the people to overcome above shortcoming, the immobilized ferric trichloride of adopting montmorillonite, and storage, the use problem of solution ferric trichloride, employing acetic acid is solvent, microwave radiation accelerating oxidation process, the reaction time is short, and product yield is higher.But still be disposable consumption oxidant, still exist consumption big, course of reaction is complicated, the problem that metal ion is residual.
Sustainable development is to prevent to pollute and energy savings after all, and environmental problem more is important in life at present.Exploitation is that the catalysed oxidation processes of oxygen source has very important significance to preventing pollution and energy savings with the air/oxygen.From the theory of Green Chemistry,, be the production route of an economy, environmental protection with the method for the synthetic benzil of air or oxygen Oxybenzene acyloin.Having the bibliographical information utilization to utilize the double salicylaldehyde ethylenediamine metal complex that contracts to be catalyst, in the DMF solvent, is oxidant with the air, under alkali condition, benzoin is carried out oxidation, and product is separated out steps such as washing and obtained the benzil product through overregulating the pH value.Catalyst can be reused three times after removing extractant, thereby reduce production cost through extraction, has reduced the discharging of waste liquid.Also having bibliographical information to adopt copper sulphate is catalyst, in pyridine solvent, accomplish the oxidation of benzoin, but the reaction time is long, and feed stock conversion is not high, the reaction dissolvent catalyst recovery difficulty that costs an arm and a leg, shortcomings such as severe reaction conditions.
Summary of the invention
The object of the invention provides a kind of bifunctional catalyst and prepares in the benzil in benzoin dehydrogenation/oxidation and uses; Concretely; Adopt solid catalyst, with the synthetic benzil of air or oxygen Oxybenzene acyloin, the reaction that dehydrogenation/oxidation takes place benzoin under certain condition generates benzil; Product selectivity is high in the course of reaction, and product separates easily.
A kind of bifunctional catalyst; Catalyst is a carrier with anion exchange resin or cationic ion-exchange resin; Valence bond closes the transition metal or the thulium of variable valency on the carrier, and the strong resultant of the transition metal of variable valency or thulium is 0.5-10wt% in the catalyst; Metallic element as oxidation catalyst on the carrier passes through chemical bond and acidity or deacidite bonding;
Can prepare by following process:
1) anion exchange resin earlier after 5-60 minute, spends deionised water, the completion preprocessing process with the NaOH of 0.1-0.5mol/L or KOH aqueous solution soaking again;
Or, cationic ion-exchange resin is earlier with HCl or the HNO of 0.1-0.5mol/L
3The H of the aqueous solution, 0.05-0.3mol/L
25O
4Or soak after 5-60 minute, spend deionised water again, accomplish preprocessing process;
2) resin handled well is added in the dimethyl formamide (DMF), add excessive terephthalaldehydic acid again, stir, reflux 3-8h, cool to room temperature leaches resin and washs with DMF;
3) reacted resin is added in the xylenes, be incorporated in the transition metal of soluble variable valency in the xylenes or the salt of thulium again in required ratio; Leach resin behind the reflux 1-5h, use dimethyl formamide (DMF) and soaked in absolute ethyl alcohol, washing after leaching respectively, oven dry gets finished product.
Terephthalaldehydic acid is 0.1-0.5 with the resin quality ratio; The mass concentration 1-7% of terephthalaldehydic acid in dimethyl formamide (DMF).
Under the acid of said bifunctional catalyst/alkali function catalytic action, benzoin generation dehydrogenation reaction generates benzil, and the water that oxidation reaction generates metering takes place under the catalytic oxidation function of this catalyst the hydrogen of taking off simultaneously.
Reaction condition is: 80-140 ℃, the air or oxygen of 0.01-0.5Mpa is an oxidant, and the solid bifunctional catalyst is adopted in reaction time >=6 hour, and benzoin generation dehydrogenation/oxidation two-step reaction generates benzil.
From the synthetic benzil of benzoin, because the particularity in the benzoin molecule, in the process of the synthetic benzil of benzoin, general what take place is the process of hydroxyl dehydrogenation, and vital process is the process that how α-OH on the phenyl ring efficiently is transformed into carbonyl.It is the key of accelerating the benzoin dehydrogenation reaction that the hydrogen that adopts oxygen or other oxidants that the benzoin molecule is taken off is quickly converted to water.In the present invention, the employing air/oxygen is an oxidant, and the hydrogen that the benzoin dehydrogenation generates combines to generate the method for water, adds the carrying out of fast response.
Further, the present invention adopts the catalyst that contains acid or alkalescence ability to promote dehydrogenation reaction speed, because entrained oh group or the oxygen room of the surface of solids helps the absorption of hydroxyl on the benzoin and the generation of dehydrogenation reaction.Catalyst comprises liquid acid, like nitric acid, and sulfuric acid, phosphoric acid etc., solid acid comprises molecular sieve, ion exchange resin.For the ease of the separation of product, guarantee low-temperature reactivity, preferred solid acid of the present invention or base catalyst more preferably adopt wide-aperture resin to carry out dehydrogenation reaction.
Further; For the ease of carrying out fast of reaction, this reaction needed adopts certain oxidation catalyst, promotes hydrogen and the oxygen reaction taken off from benzoin to generate water fast; The resin oh group recovers reset condition simultaneously, and the dehydrogenation reaction of a beginning new round.Oxidation catalyst can be the transition metal or the thulium of various variable valencies; Comprise Pd, Ru, Ag, Cu, Co, Fe, Cr, Mn, Ce; Base metal elements such as preferred Cu, Fe, Co, Cr, Mn, Ce, more preferably one or more elements such as Cu, Co, Fe and Mn are as the component of catalysis hydrogen in the catalyst and water generation oxidation reaction.
Metallic element and solid acid-base component can be used respectively, accomplish raw material jointly to the product transforming process.But in the present invention; The preferred method that adopts load; With the predecessor of metallic element,, utilize physics or chemical bonding method immobilized in the surface and duct of solid acid or solid base like slaine, metal oxygen-containing hydrochlorate, metallo-organic compound; Further remove other unnecessary components, form the bifunctional catalyst of benzoin dehydrogenation/oxidation.
Major advantage of the present invention and effect:
On the whole; The present invention adopts a kind of acidity or basic resin through the chemical bonding transition metal; Combine bifunctional catalyst, have the catalyst of dehydrogenation-oxidative function simultaneously, be used for benzoin and prepare benzil; Catalyst has easy preparation, the higher and activity stabilized characteristics of catalytic activity, and using it for normal pressure catalytic molecular oxygen Oxybenzene acyloin system, to prepare the benzil compounds be a kind of effective new method.With molecular oxygen as oxidant, low price, oxidation reaction condition is gentle; Alleviate environmental pollution, separate and purify conveniently. good reaction selectivity, feed stock conversion is high; This method has good reaction selectivity, feed stock conversion is high, and catalyst is recyclable to be applied mechanically and the technology characteristic of simple.
Further explain, set forth the present invention below, but the purposes of catalyst of the present invention is not limited through specific embodiment.
Embodiment 1:
By Co
2+Immobilized back as catalyst on the macropore styrene series anion exchange resin through chemical bond, be used for benzoin dehydrogenation-oxidation and generate benzil.
Take by weighing macroporous strong basic quaternary ammonium anion resin (D261 type) 20 grams that resin Co., Ltd of Tianjin Nankai University produces, after 30 minutes, spend deionised water again, the completion preprocessing process with the NaOH aqueous solution soaking of 0.5mol/L earlier; The resin of handling well is installed in the three-neck flask of reflux condensing tube and agitator, add 80mL dimethyl formamide (DMF) and 5 gram terephthalaldehydic acids, agitator stirs, reflux 5h, and cool to room temperature leaches resin and washs with DMF.In three-neck flask, add reacted resin, 80mL xylenes and 5 gram acetylacetonate cobalts.Leach resin behind the reflux 3h, use dimethyl formamide (DMF) and absolute ethyl alcohol fully to soak, wash after leaching respectively, 80 ℃ of oven dry down.Determining this resin, to contain the cobalt amount be 5.1%.
With pack into the fixed bed reactors of 10ml scale of above-mentioned resin, at 80 ℃, feed continuously under the air conditions of 0.2Mpa pressure, feed mass concentration and be 8% benzoin DMF solution and carry out oxidation, the air speed of control benzoin solution is 2h
-1, collect reactant liquor, chromatography benzoin conversion ratio 98%, benzil selectivity 96%.Reactant liquor reclaims DMF (rate of recovery 85%) 60 ℃ of following decompression distillation, during remaining reactant liquor inclines people 50mL cold water after the distillation, regulates pH=5-6 with hydrochloric acid; The deposition cool to room temperature of separating out, behind the suction filtration, the washing, use ethyl alcohol recrystallization again; Get yellow acicular crystal, oven dry, fusing point 94-96 ℃
Embodiment 2:
By Cu
2+Immobilized back as catalyst on superpower gel-type strong acid cation resin through chemical bond, be used for benzoin dehydrogenation-oxidation and generate benzil.
Take by weighing superpower gel-type strong acid cation resin (D-61 type) 20 grams that resin Co., Ltd of Tianjin Nankai University produces, after 30 minutes, spend deionised water again, the completion preprocessing process with the HCl aqueous solution soaking of 0.5mol/L earlier; The resin of handling well is installed in the three-neck flask of reflux condensing tube and agitator, add 80mL deionized water and 8 gram Schweinfurt greens; Agitator stirs; Reflux 5h, cool to room temperature leaches resin; Fully soak, wash with deionized water and absolute ethyl alcohol respectively after leaching, 80 ℃ of oven dry down.Determine this resin copper content 7.5%.
With pack into the fixed bed reactors of 10ml scale of above-mentioned resin, at 100 ℃, feed continuously under the air conditions of 0.5Mpa pressure, feed mass concentration and be 8% benzoin acetum and carry out oxidation, the air speed of control benzoin solution is 2h
-1, collect reactant liquor, chromatography benzoin conversion ratio 95%, benzil selectivity 98%.Reactant liquor reclaims acetic acid (rate of recovery 85%) 60 ℃ of following decompression distillation, in the remaining reactant liquor impouring 50mL cold water in distillation back, regulates pH to 5-6; The deposition cool to room temperature of separating out, behind the suction filtration, the washing, use ethyl alcohol recrystallization again; Get yellow acicular crystal, oven dry, fusing point 94-96 ℃
Embodiment 3:
Immobilized back as catalyst on the macropore styrene series anion exchange resin by the vanadium oxygen anion through chemical bond, be used for benzoin dehydrogenation-oxidation and generate benzil.
Take by weighing macroporous strong basic quaternary ammonium anion resin (D261 type) 20 grams that resin Co., Ltd of Tianjin Nankai University produces, after 30 minutes, spend deionised water again, the completion preprocessing process with the NaOH aqueous solution soaking of 0.5mol/L earlier; The resin of handling well is installed in the three-neck flask of reflux condensing tube and agitator, add the 70mL deionized water, 10mL ammoniacal liquor; 5 gram ammonium metavanadates; Agitator stirs, reflux 5h, cool to room temperature; Use dimethyl formamide (DMF) and absolute ethyl alcohol fully to soak, wash respectively after leaching resin, 80 ℃ of oven dry down.Determining this resin vanadium content is 3.4%.
With pack into the fixed bed reactors of 10ml scale of above-mentioned resin, at 120 ℃, feed continuously under the air conditions of 0.3Mpa pressure, feed mass concentration and be 8% benzoin acetonitrile solution and carry out oxidation, the air speed of control benzoin solution is 2h
-1, collect reactant liquor, chromatography benzoin conversion ratio 98%, benzil selectivity 96%.Reactant liquor reclaims acetonitrile (rate of recovery 85%) 60 ℃ of following decompression distillation, during remaining reactant liquor inclines people 50mL cold water after the distillation, regulates pH to 5-6; The deposition cool to room temperature of separating out, behind the suction filtration, the washing, use ethyl alcohol recrystallization again; Get yellow acicular crystal, oven dry, fusing point 94-96 ℃
Embodiment 4:
By Fe
3+Immobilized back as catalyst on chelating resin through chemical bond, be used for benzoin dehydrogenation-oxidation and generate benzil.
Take by weighing chelating resin (LS-5000 type) 20 grams that Xi'an blue dark extraordinary resin Co., Ltd produces, spend deionised water three times, accomplish preprocessing process; The resin of handling well is installed in the three-neck flask of reflux condensing tube and agitator, add 80mL deionized water and 10 gram FeCl
36H
2O, agitator stirs, reflux 5h, cool to room temperature leaches resin, fully soaks, washs with deionized water and absolute ethyl alcohol respectively after leaching, 80 ℃ of oven dry down.Determine this resin iron-holder 6.3%.
With pack into the fixed bed reactors of 10ml scale of above-mentioned resin, at 140 ℃, feed continuously under the air conditions of 0.5Mpa pressure, feed mass concentration and be 8% benzoin acetum and carry out oxidation, the air speed of control benzoin solution is 1h
-1, collect reactant liquor, chromatography benzoin conversion ratio 90%, benzil selectivity 94%.Reactant liquor reclaims acetic acid (rate of recovery 85%) 60 ℃ of following decompression distillation, in the remaining reactant liquor impouring 50mL cold water in distillation back, regulates pH=5-6 with hydrochloric acid; The deposition cool to room temperature of separating out, behind the suction filtration, the washing, use ethyl alcohol recrystallization again; Get yellow acicular crystal, oven dry, fusing point 94-96 ℃
Embodiment 5:
By Mn
2+Immobilized back as catalyst on catalytic resin through chemical bond, be used for benzoin dehydrogenation-oxidation and generate benzil.
Take by weighing catalytic resin (LS-51) 20 grams that Xi'an blue dark extraordinary resin Co., Ltd produces, the HCl aqueous solution soaking of at first using 0.5mol/L spends deionised water after 30 minutes again, accomplishes preprocessing process; The resin of handling well is installed in the three-neck flask of reflux condensing tube and agitator, add 80mL deionized water and 8 gram manganese sulfates; Agitator stirs; Reflux 5h, cool to room temperature leaches resin; Fully soak, wash with deionized water and absolute ethyl alcohol respectively after leaching, 80 ℃ of oven dry down.Determine this resin manganese content 7.5%.
With pack into the fixed bed reactors of 10ml scale of above-mentioned resin, at 100 ℃, feed continuously under the air conditions of 0.2Mpa pressure, feed mass concentration and be 8% benzoin DMF solution and carry out oxidation, the air speed of control benzoin solution is 2h
-1, collect reactant liquor, chromatography benzoin conversion ratio 94%, benzil selectivity 97%.Reactant liquor reclaims DMF (rate of recovery 85%) 60 ℃ of following decompression distillation, in the remaining reactant liquor impouring 50mL cold water in distillation back, regulates pH=5-6 with hydrochloric acid; The deposition cool to room temperature of separating out, behind the suction filtration, the washing, use ethyl alcohol recrystallization again; Get yellow acicular crystal, oven dry, fusing point 94-96 ℃
Claims (8)
1. bifunctional catalyst is characterized in that:
Catalyst is a carrier with anion exchange resin or cationic ion-exchange resin, and valence bond closes the transition metal or the thulium of variable valency on the carrier, and the bonded amount of the transition metal of variable valency or thulium is 0.5-10wt% in the catalyst; Metallic element as oxidation catalyst on the carrier passes through chemical bond and acidity or deacidite bonding;
Can prepare by following process:
1) anion exchange resin earlier after 5-60 minute, spends deionised water, the completion preprocessing process with the NaOH of 0.1-0.5mol/L or KOH aqueous solution soaking again;
Or, cationic ion-exchange resin is earlier with HCl or the HNO of 0.1-0.5mol/L
3The H of the aqueous solution, 0.05-0.3mol/L
2SO
4Or soak after 5-60 minute, spend deionised water again, accomplish preprocessing process;
2) resin handled well is added in the dimethyl formamide (DMF), add excessive terephthalaldehydic acid again, stir, reflux 3-8h, cool to room temperature leaches resin and washs with DMF;
3) reacted resin is added in the xylenes, be incorporated in the transition metal of soluble variable valency in the xylenes or the salt of thulium again in required ratio; Leach resin behind the reflux 1-5h, use dimethyl formamide (DMF) and soaked in absolute ethyl alcohol, washing after leaching respectively, oven dry gets finished product.
2. bifunctional catalyst according to claim 1 is characterized in that: terephthalaldehydic acid is 0.1-0.5 with the resin quality ratio.
3. bifunctional catalyst according to claim 1 is characterized in that: the mass concentration 1-7% of terephthalaldehydic acid in dimethyl formamide (DMF).
4. bifunctional catalyst according to claim 1 is characterized in that:
The transition metal of variable valency or thulium are a kind of among Pd, Ru, Ag, Cu, Co, Fe, Cr, Mn, the Ce or more than two kinds, they are as the component of catalysis hydrogen in the catalyst and water generation oxidation reaction.
5. bifunctional catalyst according to claim 4 is characterized in that:
The transition metal of said variable valency or thulium are a kind of among Cu, Fe, Co, Cr, Mn, the Ce or more than two kinds.
6. bifunctional catalyst according to claim 4 is characterized in that: the transition metal of said variable valency or thulium are a kind of among Cu, Co, Fe, the Mn or more than two kinds.
7. any one said bifunctional catalyst prepares in the benzil in benzoin dehydrogenation/oxidation and uses among the claim 1-6, it is characterized in that:
Under the acid of any one catalyst in claim 1-6/alkali function catalytic action, benzoin generation dehydrogenation reaction generates benzil, and the water that oxidation reaction generates metering takes place under the catalytic oxidation function of this catalyst the hydrogen of taking off simultaneously.
8. according to the application of the said bifunctional catalyst of claim 7; It is characterized in that: reaction condition is: 80-140 ℃, the air or oxygen of 0.01-0.5Mpa is an oxidant, reaction time >=6 hour; Adopt the solid bifunctional catalyst, benzoin generation dehydrogenation/oxidation two-step reaction generates benzil.
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| CN103467265A (en) * | 2013-09-16 | 2013-12-25 | 山东大学 | Preparation method of 4,4'-di-trifluoromethyl benzil |
| CN103508508A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Application of porous biomass resin in adsorptive separation |
| CN108404991A (en) * | 2018-05-08 | 2018-08-17 | 宁波大学 | A kind of catalysis oxidation purposes of sulfaquinoxaline cobalt compound |
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| CN103467265A (en) * | 2013-09-16 | 2013-12-25 | 山东大学 | Preparation method of 4,4'-di-trifluoromethyl benzil |
| CN103467265B (en) * | 2013-09-16 | 2015-05-13 | 山东大学 | Preparation method of 4,4'-di-trifluoromethyl benzil |
| CN109317199B (en) * | 2017-07-31 | 2021-12-21 | 中国石油化工股份有限公司 | Nitrate radical chemical reduction catalyst and preparation method thereof |
| CN109317198A (en) * | 2017-07-31 | 2019-02-12 | 中国石油化工股份有限公司 | The preparation method of effective catalyst applied to electronation sewage nitrate |
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| CN109317199A (en) * | 2017-07-31 | 2019-02-12 | 中国石油化工股份有限公司 | Nitrate anion electronation catalyst and preparation method thereof |
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| CN109317198B (en) * | 2017-07-31 | 2021-08-10 | 中国石油化工股份有限公司 | Preparation method of high-efficiency catalyst applied to chemical reduction of sewage nitrate |
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